Computational mechanistic investigation of the Fe + CO2 -> FeO plus CO reaction

Author(s)

Vicentini, Eduardo Dias ^[1] ; de Lima Batista, Ana P. ^[2] ; Sampaio de Oliveira-Filho, Antonio G. ^[1]

Affiliation

^[1] Univ Sao Paulo, Dept Quim, Lab Computac Espectroscopia & Cinet, Fac Filosofia Ciencias & Letras Ribeirao Preto, BR-14040901 Ribeirao Preto, SP - Brazil

^[2] Univ Sao Paulo, Fac Filosofia Ciencias & Letras Ribeirao Preto, Lab Atividade Biol & Quim Supramol Compostos, Dept Quim, LABIQSC2, BR-14040901 Ribeirao Preto, SP - Brazil

• Document type: Journal article
• Source: Physical Chemistry Chemical Physics; v. 22, n. 29, p. 16943-16948, AUG 7 2020.
• Web of Science Citations: 0

Abstract

We report a computational study of the mechanism and determination of the rate constants of the Fe + CO2 -> FeO + CO reaction, in the 1000-3000 K temperature range, at the CCSD(T)/CBS//B3LYP/def2-TZVP level of theory. The overall rate constant was obtained by a Kinetic Monte Carlo simulation. The calculated rate constant, at 2000 K, is 9.72 x 10(-13) cm(3) molecule(-1) s(-1), in agreement with experimental measurements: 2.97 x 10(-13) cm(3) molecule(-1) s(-1) {[}A. Giesen et al., Phys. Chem. Chem. Phys., 2002,4, 3665] and 1.13 x 10(-13) cm(3) molecule(-1) s(-1) {[}V. N. Smirnov, Kinet. Catal., 2008,49, 607]. Our study shows that this reaction follows a complex mechanism, with multiple reaction paths contributing to the overall rate, and that CCSD(T) accurately describes this transition metal reaction. (AU)

• FAPESP's process: 15/11714-0 - Reactivity, transformation, fixation, and spectroscopy of systems involving CO2
• Grantee: Antonio Gustavo Sampaio de Oliveira Filho
• Support Opportunities: Regular Research Grants
• FAPESP's process: 17/18238-4 - Catalytic C-H activation reactions: computational study aiming atom efficiency in CO2 fixation
• Grantee: Ana Paula de Lima Batista
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 17/11631-2 - CINE: computational materials design based on atomistic simulations, meso-scale, multi-physics, and artificial intelligence for energy applications
• Grantee: Juarez Lopes Ferreira da Silva
• Support Opportunities: Research Grants - Research Centers in Engineering Program